WO2014207171A1 - Solar protection glazing - Google Patents

Solar protection glazing Download PDF

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Publication number
WO2014207171A1
WO2014207171A1 PCT/EP2014/063634 EP2014063634W WO2014207171A1 WO 2014207171 A1 WO2014207171 A1 WO 2014207171A1 EP 2014063634 W EP2014063634 W EP 2014063634W WO 2014207171 A1 WO2014207171 A1 WO 2014207171A1
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WO
WIPO (PCT)
Prior art keywords
preferably
nm
characterized
glazing according
glazing
Prior art date
Application number
PCT/EP2014/063634
Other languages
French (fr)
Inventor
Stijn Mahieu
Gaëtan DI STEFANO
Marc Hauptmann
Jacques Dumont
Original Assignee
Agc Glass Europe
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE201300453 priority Critical
Priority to BEBE2013/0453 priority
Application filed by Agc Glass Europe filed Critical Agc Glass Europe
Publication of WO2014207171A1 publication Critical patent/WO2014207171A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3681Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3626Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3649Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366Low-emissivity or solar control coatings

Abstract

The invention relates to a solar protection glazing comprising, on at least one of the faces of a glass substrate, a multi-layer stack comprising at least one layer absorbing solar radiation of at least 3 nm and dielectric coatings surrounding said solar radiation absorbing layer. According to the invention, the light reflection of the glass substrate coated with the multi-layer stack, measured on the substrate side, is at least 20% and is at least two times the light reflection of the glass substrate coated with the multi-layer stack measured on the stack side, and the reflection colour on the substrate side has a colorimetric coordinate value a* of less than 2 and a colorimetric coordinate value b* of less than 5. The invention is particularly useful as an automobile glazing, in particular on the roof thereof, as a building glazing or as a household oven.

Description

solar control glazing.

1. Field of the Invention.

The field of the invention is that of solar control glazing consisting of a glass substrate carrying a multi-layer stack including at least one thin layer provides the said solar control properties. A said functional layer are associated dielectric layers which function in particular to adjust the reflective properties, transmission, shade and protection against mechanical or chemical alterations of the stack properties.

Specifically, the invention relates to glazing intended to fill the buildings but also motor vehicles. According to these uses certain properties required may differ.

The functionality of solar control glass are multiple. Concerning, in particular heating of prevention of the inside of the cabin of a motor vehicle, in particular vis-à-vis solar radiation passing through a transparent roof, or a building exposed to solar radiation when it is intense enough. According to some embodiments, the heating of prevention can be achieved while maintaining an appropriate light transmission.

In the case especially glazing for buildings, but also for the car, it is increasingly often asked whether that could withstand heat treatments without their particular color in reflection is changed significantly. The goal is to have windows side by side heat-treated and others that have not been without color differences are obvious.

In the following description, the optical properties are defined for the substrate glass which is glass "float" ordinary clear 4 mm thick. The choice of substrate obviously influences these properties. For ordinary clear glass the light transmission under 4 mm in the absence of layer is approximately 90% and the reflection to 8%, measured with a source according to the illuminant "daylight" standardized by the D65 ICE and under a solid angle of 2 °. The energy measures, for their part, are made according to EN 410.

The term "glass" is understood to mean an inorganic glass. By this is meant a glass thickness at least greater than or equal to 0.5 mm and at most less than or equal to 20.0 mm, preferably at least greater than or equal to 1.5 mm and at most less than or equal to 10.0 mm comprising silicon as one of the essential constituents of the glass. For some applications, the thickness may for example be 1.5 mm or 1.6 or 2 or 2.1 mm. For other applications, it will be for example around 4 or 6 mm. Preferred glasses clear silica-soda-lime, extra clear or colored in the mass or on the surface.

The presence of a multilayer stack can cause color problems. Most often the market demand that glazing offers, both in transmission and in reflection, as neutral a color as possible and therefore gray appearance. slightly green or blue colorations are possible. However, much more pronounced shades, for example blue or green, are also sometimes required to meet specific aesthetic criteria. Multilayer stacks, especially the natures indices and thicknesses of the dielectric layers flanking the functional layers are chosen in particular to control these colorations.

The automotive glazing, in theory can be many to give them a better including thermal insulation property. In fact these achievements are exceptional. The vast majority of these windows consists of single glazing is monolithic or laminated. The multilayer stack may be on one side which is not protected from mechanical or chemical stresses. The stacks in question must therefore have very good resistance to these possible attacks. In practice to limit the risk of tampering, multilayer stacks are normally on the side of the window facing the passenger. But even in this position they must offer a very good mechanical strength.

layer systems according to the invention still have to lend to formatted glazing. Those used in vehicles are particularly subject to heat treatment during forming, especially the bending of glass sheets, or during quenching for imparting particular their enhanced mechanical properties. The layers used in the invention must withstand these treatments without their properties are degraded. Treatments of this type require temperatures that exceed 600 ° C during ten minutes. Subject to these temperatures the layers should retain their qualities and properties.

The aesthetic aspect is also of great commercial importance for sun protection glazing. Indeed, it is not only required that the glazing has thermal properties sunscreen, also asked that participates in the aesthetic quality of the whole of which it is part. These aesthetic criteria can sometimes lead to some conflict situations with some obtaining better thermal properties.

2. Solutions of the prior art.

The prior art provides sunscreen glazing having a solar absorbing layer surrounded by dielectric layers.

Patent Application EP 779 255 Al describes a glass substrate coated with a solar absorbing layer NiCr surrounded by dielectric layers Si 3 N 4 that can withstand high temperature heat treatment.

U.S. Patent 6,852,419 B2 discloses a solar control glazing comprising a stack formed of a solar absorbing layer NbCrNx surrounded by dielectric coating Si 3 N 4. This stack is capable of withstanding a high temperature heat treatment.

Patent application FR 2869606 Al discloses a solar control glazing comprising a stack formed of a solar absorbing layer Nb surrounded by dielectric coating Si 3 N 4. The stack can also supported a high temperature heat treatment.

Earlier proposals meet at least in part with the requirements of the intended use of the glazing according to the invention, in particular sunscreen thermal properties. Nevertheless, aesthetic property must be improved to satisfy certain commercial applications.

3. Objectives of the invention

The invention particularly aims to overcome this drawback of the prior art.

More specifically, an object of the invention is to provide a glazing provided with a multilayer stack in sunscreen property that provides a more favorable aesthetic appearance to the assembly in which it is installed, and which is simple and inexpensive to manufacture , in particular with a minimum of layers.

An object of the invention, in at least one of its embodiments, is to provide a glazing provided with a multilayer stack to sunscreen and cosmetic properties that is capable of undergoing a heat treatment at elevated temperature, and toughening type / or bending, preferably without significantly changing its hue, especially in reflection substrate side, so that a heat-treated glass can not be juxtaposed with his version heat treated without an observer can detect a significant difference of overall appearance.

The invention, in at least one of its embodiments, also seeks to provide a glazing provided with a multilayer stack having a good stability of the thermally, chemically and mechanically.

The invention, in at least one of its embodiments, also seeks to provide a glazing including multilayer stack can be placed in external position without necessarily having to be protected from the external environment by another substrate.

4. Presentation of the invention. The invention relates to a transparent glazing solar control having on at least one of the faces of a glass substrate a transparent multilayer stack comprising a solar absorbing layer of at least 3 nm and a geometrical thickness of the first and second dielectric coatings surrounding said layer absorbing solar radiation, characterized in that the light reflection of the glass substrate coated with the multilayer stack measured from the substrate side is at least 20% and is at least twice the light reflection the glass substrate coated with the multilayer stack measured from the side of the stack, and in that the dyed substrate side has a reflection value of the color coordinate a * (L * a * b * CIE) of less than 2 and value of the color coordinate b * of less than 5.

This new feature related to the light reflection is contrary to the current practice whereby light reflections are not very different from each other.

It was discovered that this combination of feature is advantageous in that it provides, surprisingly, a significant and appreciated aesthetic effect, while maintaining sufficient visibility from inside the space enclosed by the glass towards outside and avoiding an unpleasant mirror seen from inside.

Absorbing solar radiation layer, that is to say, the functional layer of the stack has a geometrical thickness of at least 3 nm, preferably at least 5 nm and preferably at least 10 nm. This thickness is instrumental in the light transmission and solar factor of the glazing. The thickness should be sufficient, at least 3 nm, to obtain a significant effect. Its setting is then used to adjust the properties to the desired values.

By "solar absorbing layer" is meant, in the present invention, a layer formed of a metal or a metal alloy, or a metal nitride or a metal alloy nitride, having an average extinction coefficient between 380 nm and 750 nm, greater than 0.8, preferably greater than 1.2 and preferably greater than 1.4. The dielectric coatings flanking the solar absorbing layer preferably comprise at least one layer of a dielectric material based on a compound selected from silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, mixed aluminum-silicon nitrides, silicon oxynitride and aluminum oxynitride,

The layer or layers forming the dielectric coating material may also be doped layers with at least one other element, containing up to about maximum 10% by weight of the other element, the latter having dielectric properties in practice not differing layers consisting of said dielectric material. For example, when the layer is silicon nitride thereof can contain up to 10% by weight of aluminum (for example, layers deposited by sputtering method from a silicon target containing up to 10% weight of aluminum). The dielectric coatings can also consist of several individual layers comprising or consisting essentially of the same materials. The dielectric layers can be deposited by well known called PECVD ( "Plasma-Enhanced Chemical Vapor Deposition") or chemical vapor deposition, plasma enhanced.

The layer absorbing solar radiation, which is the functional layer, is surrounded by dielectric coatings. This is not to say that these dielectric coatings must necessarily be in direct contact with the functional layer, because there may be thin interlayers for various reasons, but they must be in the immediate vicinity of the functional layer. Each of the dielectric films may be a monolayer, but each of the dielectric films may also comprise several layers of different materials. However, each of said dielectric coatings always contain preferably at least 10 nm of a dielectric material selected from oxide, oxynitride or silicon nitride, and oxide, oxynitride or nitride 'aluminum. Other dielectric materials may be materials based on oxides of Zn, Sn, Ti, Zr, Nb, or other dielectric materials well known in the art, and in particular zinc stannate. Preferably, the light reflectance of the glass substrate coated with the multilayer stack measured from the substrate side is at least 2.5 times, preferably at least 3 times, and preferably at least 3.5 times, or even 4 times higher than the light reflectance of the glass substrate coated with the multilayer stack measured from the side of the stack. Preferably, the substrate side measured light reflectance is higher by at least 14%, at least 16%, preferably at least 20% and preferably at least 25%, at the light reflection side stacking measured

One can thus obtain a very high external light reflection providing a marked aesthetic effect while maintaining good visibility through the glazing seen from the interior of the space closed by the glass.

According to a preferred embodiment of the invention, the measured light reflection of the substrate side is at least 27%, preferably at least 30%, and preferably at least 35%.

To achieve high light reflection of the substrate side and a high difference between the reflections on both sides of the coated substrate, there are different possibilities of realization. An effective way within the transparent glazing which are the subject of the invention is to favorably influence the interference effect between the layers. Again, various options can be considered. But the interference effect strongly influences the colors obtained in reflection and transmission. Preferably, the optical thickness L of the virtual first dielectric coating disposed between the substrate and the solar radiation absorbing layer, to a value less than or equal to 25 nm or even less than or equal to 20 nm, advantageously less than or equal to 17 nm, and preferably less than or equal to 15 nm. This feature facilitates obtaining a high light reflection from the substrate side, while having the ability to maintain the required color. Preferably, the optical thickness L of the virtual first dielectric coating is between 5 and 20 nm, preferably between 10 and 20 and preferably between 12 and 16 nm. This provides a good compromise between a high reflection difference between the two sides, a relatively neutral color of the substrate side and a good resistance to thermal treatment.

The virtual optical thickness L of a dielectric coating is defined in the context of the present invention, as the sum of the geometrical thicknesses (physical) in nm of each of the dielectric material forming the dielectric coating multiplied by the refractive index n at 550 nm of each of the materials decreased by the refractive index of the gas from the surrounding atmosphere. For a coating formed of many different dielectric materials, the value L is obtained by summing the results of multiplications of the geometrical thickness (e) in nm of each of the materials by the value obtained by subtracting the index value of refraction at 550 nm of the atmosphere, generally air, or the value 1, the refractive index n at 550 nm of the corresponding material [L = ex (n D n air 550 .- 550) n D 550 = refractive index of the material at 550 nm].

Preferably, the second dielectric coating, disposed beyond the solar absorbing layer relative to the substrate, has a virtual total thickness L of between 35 and 85 nm, preferably between 40 and 70 nm and preferably between 45 and 65 nm and most preferably between 50 and 60 nm, and the refractive index n means the coating is greater than 1.5. This feature allows both to easily achieve both high external reflection and low internal reflection, while having an acceptable color in external reflection and aesthetically pleasing.

Advantageously, the optical thickness L of the virtual first dielectric coating is between 10 and 20 nm, and the virtual total thickness L of the second dielectric film is between 45 and 65 nm, preferably between 50 and 60 nm. the best conditions are thus met to obtain a high reflection side substrate with a low-reflection layer side and a relatively neutral tint in reflection on the substrate side.

Preferably, the virtual thickness L of the first dielectric film, disposed between the substrate and the solar radiation absorbing layer is at least one and a half times thicker or thinner than the virtual thickness L of the last dielectric coating of the multilayer stack disposed above the infrared-absorbing layer with respect to the substrate. This feature facilitates the adaptation of interference effects. Preferably, the virtual thickness L of the first dielectric film, disposed between the substrate and the solar radiation absorbing layer is at least one and a half times thinner, preferably twice, and preferably three times, thinner than the thickness virtual the last dielectric coating of the multilayer stack disposed above the infrared-absorbing layer with respect to the substrate.

As already indicated above, a preferred dielectric materials for forming said dielectric coatings, and in particular the second coating disposed over the functional layer, is silicon nitride which has a refractive index between 1.9 2.05. However, as also previously explained, the dielectric coating layers can include other dielectric materials as silicon nitride. Preferably, the dielectric material coating disposed over the solar absorbing layer comprises a material having a high refractive index, greater than 2, and advantageously greater than 2.1. In the context of the present invention, the dielectric high refractive index is preferably a material which supports the heat treatment without significant structural change. A specific example of such a material is doped titanium oxide or a mixture, for example with zirconium or niobium, in particular a mixture of titanium oxide and zirconium oxide in an amount of 40 to 60% each. Another example of such a material is zirconium oxide. Preferably, this high-index material is disposed between the solar absorbing layer and the outermost dielectric layer of the stack.

The solar absorbing layer may be a nitride, such as TiN, CrN, WN, NbN, TaN, ZrN or NiCrN, or a mixture of these nitrides. These nitrides may be partially oxidized. Preferably, the solar absorbing layer is an essentially metallic layer such as NiCr, W, Nb, Zr, Ta, stainless steel, or alloys based on Ni and / or Cr. Preferably, the solar absorbing layer is a metallic layer based on a metal having an extinction coefficient k between 2 and 4.5 in the range of the visible spectrum from 380 nm to 750 nm.

Preferably, the solar absorbing layer is a layer of NiCr-based alloy and W, based on an alloy of Cr and Zr, based alloy of W and Zr, or Cr, or an alloy based W and Ta. These alloys have proven very advantageous to form solar absorbing layers that can easily withstand the high temperature heat treatment without significant deterioration of their properties. These alloys can also contain nested one additional metal selected from Ti, Nb, Ta, Ni and Sn.

Some preferred examples of implementation of the invention, the absorbent layer solar radiation a layer of a NiCrW alloy surrounded by a first dielectric coating consisting essentially of silicon nitride with a geometrical thickness between 10 and 20 nm and a second dielectric coating consisting essentially of silicon nitride with a geometrical thickness between 50 and 65 nm. According to other preferred examples, the solar absorbing layer is a layer of NiCr alloy surrounded by a first dielectric coating consisting essentially of silicon nitride with a geometrical thickness between 10 and 20 nm and a second dielectric coating consisting essentially of silicon nitride with a geometrical thickness between 55 and 60 nm. According to still other preferred examples, the solar absorbing layer is a layer of CrZr alloy surrounded by a first dielectric coating consisting essentially of silicon nitride with a geometrical thickness between 10 and 20 nm and a second dielectric coating consisting essentially of silicon nitride with a geometrical thickness between 60 and 66 nm.

Preferably, the solar absorbing layer has a geometrical thickness of between 3 and 40 nm, or between 3 and 30 nm, preferably between 5 and 25 nm. Preferably, the solar absorbing layer preferably has a geometrical thickness between 10 and 25 nm, and advantageously between 12 and 22 nm. Such a solar absorbing layer is adequate to form the functional layer of the multilayer stack, that is to say the basic layer to obtain the solar control properties. Can be obtained easily and multilayer stacking extremely simple and very durable.

Preferably, the two dielectric films sandwiching the solar absorbing layer is based on silicon nitride or aluminum nitride. This ensures very good protection of the metal layer absorbing solar radiation during the high temperature heat treatment.

Other additional layers may be added, either directly on the substrate or as an outer protective layer, or within the stack of the multilayer stack, in order to provide the multilayered stack of the base properties and / or additional protection, such as for example an additional external protection against mechanical or chemical attack, for example formed by a mixture of titanium oxide and zirconium oxide, a barrier against the alkali from the substrate, different optical properties, improved electrical properties of the metallic layers, an improvement in the deposition rate, or any additional functions. The additional layers, however, should preferably be chosen so that they do not disrupt the ability of the multilayered stack to undergo a high-temperature heat treatment. In particular, it is advantageous to ensure that such additional layers do not undergo substantial changes, including structural changes during the heat treatment to prevent them cause changes in the optical properties of the multilayer stack during the heat treatment.

Heat treatments, including bending / toughening type, may also induce more or less significant changes in the optical properties including shades. Preferably, these changes must be minimized so that heat-treated or not the windows have an almost unchanged appearance. Traditionally measuring variations is carried out from the coordinates of the CIELAB system. The change is expressed by the term denoted ΔΕ *, an expression corresponding to the formula:

ΔΕ * = (U * 2 * 2 + Aa + Ab * 2) 1/2

Where G * represents the difference between the color coordinates L * of the glass before and after heat treatment,

Aa * represents the difference between the colorimetric coordinates a * of the pane before and after heat treatment,

* Ab represents the difference between b * colorimetric coordinates of the pane before and after heat treatment,

More particularly, and preferably, the glazing according to the invention has a color variation in reflection side substrate face, AE * rG:

AE * = rg (G * rg rg 2 + 2 + Aa * Ab * rg 2) 1/2

less than 8, preferably less than 5, preferably less than 3, and even preferably less than 2, when said glass is subjected to a temperature of at least 630 ° C and at most 670 ° C for 7 minutes.

The invention is particularly useful for obtaining high stability of the tint in reflection on the substrate side of a thermal treatment at high temperature tempering and / or bending. The dyed substrate side is thinking, in many applications, the most noticeable tint of an observer, because it is this face that attracts attention as the glazing operating conditions. The slightest difference in hue is more readily apparent.

Additionally, the glazing according to the invention also preferably a colorimetric change transmission, ΔΕ:

ΔΕ = (G + 2 Aa \ 2 + Ab \ 2) 1/2

less than 8, preferably less than 5, more preferably less than 3, when said glass is subjected to a temperature of at least 630 ° C and at most 670 ° C for 7 minutes.

The glazing according to the invention additionally or not the two preceding properties, color variation in reflection face side layer, AE * rc, such that: AE * rc = (AL * 2 + Aa * rc rc 2 + Ab * rc 2) 1/2

less than 8, preferably less than 5, when said glass is subjected to a temperature of at least 630 ° C and at most 670 ° C for 7 minutes.

According to a particular embodiment, the glazing according to the invention is such that the thickness of the solar absorbing layer is selected so that the light transmission for a substrate consisting of clear glass of 4 mm thickness is at least 2% and at most equal to 75%. In the case of use as a motor vehicle roof, the light transmission is preferably between 2 and 10%, advantageously between 6 and 8%. In the case of application in the building, the light transmission is preferably between 10 and 70%, advantageously between 10% and 60%, favorably between 10 and 50% and preferably between 20 and 40%. Indeed, the absorbent layer solar radiation control the light and energy transmission, so that the more it is thick more it absorbs.

The glazing according to the invention find various applications by adapting their properties by adjusting layers and in particular of their thicknesses.

The glazing according to the invention can be part of double glazing in which case the multi-layer stack may be disposed in the space between the two glass sheets, which limits the risks of particular mechanical alteration. However one of the significant features of multilayer stacks proposed for the glazing according to the invention is their both mechanical and chemical resistance. This strength is such that they can be used with the multilayer stack exposed without further protection. In the latter case the glazing unit may as well consist of a single glass sheet, multilayer stacks being applied on one side of this sheet. It can also be a laminated glazing comprising two sheets of glass, or more, the sheets being joined together by interlayers of thermoplastic material according to the conventional techniques in this field.

In these applications on a single glazing the multilayer stack is not protected from the environment. Even in the case of laminated glazing, the layers may be on an outer face so that they can play their role in controlling energy transmission by acting on the emissivity of the surface.

The glazing according to the invention finds its application as glazed element for a motor vehicle: roof, side window, rear window (the multilayer stack preferably being on the exposed face towards the passenger compartment) and building glazing element.

The glazing according to the invention also finds application as a glazed element of household appliance such as a furnace door, where it can also bring an aesthetic effect sought. It is resistant to various chemical and / or mechanical due to this particular type of application.

As already indicated above several times, the glazing according to the invention is of course also its application as a glazed element of a building. In this case of application, the glazing may form a double or triple glazing with the multilayer stack disposed facing the closed space inside the multiple glazing. The glazing may also form a laminated glazing including multilayer stack may be in contact with the thermoplastic adhesive material between the substrates, in general, the PVB. The glazing according to the invention is however particularly useful when the multilayer stack is facing the external environment, be it a single glazing or laminated glazing, but also possibly a multiple glazing.

Of course, the glass substrate may be a glass tinted in the mass, such as gray glass, blue or green, to absorb more solar radiation, or to form a private area at low light transmission in order to conceal the interior vehicle or an office in a building, external looks.

5. Description of preferred embodiments of the invention

Examples of glazings according to the invention but also comparative examples ( "R") are given in Table I below. The optical properties are defined for the substrate glass which is glass "float" ordinary clear 4 mm thick. The layers are in the order, from left to right, starting from the glass. The approximate geometrical thicknesses are expressed in nm.

Table I: Examples of glazing according to the invention and comparative performance glazing according to the invention with glazing of the prior art, the coatings being deposited on clear glass having a thickness of 4 mm. The light transmission (TL) and the light reflection layer side (Rc) and glass side (Rg) are also shown (in%) for some examples.

Absorbing solar radiation layers and dielectric layers are applied by a sputtering technique ( "sputtering") under conventional conditions for this type of technique. Alternatively, the dielectric layers are applied by the well-known known as PECVD technique ( "Plasma-Enhanced Chemical Vapor Deposition") or chemical vapor deposition assisted by plasma.

The dielectric layers of silicon nitride are produced from metallic targets in an atmosphere consisting of a mixture of argon (30- 70%) and nitrogen (70-30%) at a total pressure of 4mTorr (0, 53Pa). The layers of chromium-zirconium (40 wt% Cr and 60% of zirconium in the CrZr alloy), the layers of nickel-chrome (Nickel / Chrome 80/20) and the layers of nickel-chrome (Nickel / Chrome 80/20) -tungstène (50% by weight of NiCr and 50% of W in the alloy NiCrW) are deposited from metal cathodes in single argon atmosphere. The dielectric layers of silicon oxide are produced starting from a silicon target in an atmosphere containing argon and oxygen.

On the samples by measuring the light transmission TL and the light reflection from the substrate side with illuminant D65, 2 °. The colorimetric coordinates L *, a *, b *, CIE, were also measured before and after heat treatment ave illuminant D65, 10 °. The angle at which measurements are made is 8 °.

The samples are subjected to a heat treatment comprising holding at 670 ° C for 8 min and 30 sec. Changes in transmission and reflection in ΔΕ * are also given in Table I. In this table, the SiN numerals denote silicon nitrides without representing a chemical formula, provided that the products obtained are not necessarily strictly stoichiometric but are those obtained in the deposition conditions indicated and are neighbors stoichiometric products. The SiN layer may contain up to about maximum 10% by weight of aluminum from the target. The SiN layer has a refractive index n = 2.03 to 550 nm. The dielectric coating may also consist of several individual layers comprising or consisting essentially of the same materials.

Figures in parentheses are the physical thicknesses of the various layers nm. Properties (in% for light transmission and reflection) are provided as monolithic glazing after heat treatment. The term "TZO" is a mixed oxide comprising 50% TiO 2 and 50% ZrO 2. TZO layers have a refractive index n = 2.3 at 550 nm.

Ex. Stacking multilayer TL Rc Rg ΔΕ% AE * Rc

RI SiN (20) / NiCrW (8.5) / SiN (35) 31.6 19.3 24.6 0.7 1.9 1.7

R2 SiN (20) / NiCrW (13.7) / SiN (35) 19.9 25.7 32.7 1.3 1.3 0.9

R3 SiN (20) / NiCrW (22) / SiN (35) 10.19 33 41.4 3 2.1 0.3

R4 SiN (87) / NiCrW (13.7) / SiN (30) 20.67 31.9 21.6 2 3 0.8

1 sin (13) / CrZr (6.7) / SiN (50.6) 33.8 7.4 34.6

2 SiN (13) / CrZr (10.3) / sin (46.7) 23.5 13.8 39.9

3 SiN (79.2) / CrZr (14) / sin (50.1) 22.2 15 30.9

4 SiN (16.4) / CrZr (7.6) / TZO 31.3 8.6 39

(24 l) / SiN (25)

SiN (13) / CrZr (II, 6) / TZO

5 (21.4) / SiN (25) 21.6 12.7 44.7

SiN (13.4) / CrZr (21.3) / TZO

6 (18.2) / sin (31.3) 10.8 15.7 51.2 SiN (78) / CrZr (14.7) / TZO

7 (22.5) / sin (25.1) 22 13.4 33

8 SiN (15) / NiCrW (9.8) / SiN (50.6) 32.5 6 34.6 0.6 6 1

9 SiN (15) / NiCrW (15.4) / sin (48.2) 21.6 11.5 40.1 0.9 5.3 0.7

10 SiN (15) / NiCrW (24.5) / SiN (48) 10.5 17.5 45 2.1 3.7 1.5

11 sin (78.4) / NiCrW (18) / sin (49.5) 20.4 14.9 30.9 1.2 4.9 0.7

12 SiN (15) / NiCrW (10.1) / TZO 32.4 6.1 39.2 1.2 3.1 0.9

(29.7) / SiN (20)

SiN (15) / NiCrW (16.2) / TZO

13 (27.2) / SiN (20) 21.1 9.2 45.1 0.9 2.6 0.9

SiN (15) / NiCrW (25) / TZO

14 (13.2) / SiN (34.7) 10.8 14.9 47.7 0.4 2.8 0.6

SiN (75.4) / NiCrW (18.9) / TZO

15 (23.7) / sin (23.6) 21.3 11.9 33.5 1.4 1.4 0.3

The color coordinates (L * a * b * CIE) of Comparative Examples and certain Examples of the invention are given in Table II below in reflection and transmission substrate side.

Table II

Glass side reflection R G Transmission

Ex. L * a * b * L * a * b *

RI 56.8 -1.97 -3.5 63.14 -0.81 -4.51

R2 63.93 -1.66 -0.86 51.89 -0.98 -5.1

R3 70.38 -1.32 2.96 38.28 -1.08 -2.49

R4 54.23 -3.43 -17.41 52.52 -0.45 2.38

1 65.28 -3.2 -1.74 64.02 -2.18 -1.93 2 69.45 -2.66 -0.2 53.77 -2.39 -2

3 62.41 -3.08 -12.22 52.59 -2.58 7.41

4 68.7 -3.3 -2.0

5 72.6 -2.7 -1.3

6 75.5 -1.7 6

7 64.6 -3.1 -11.9

The examples according to the invention have an external reflection, from the side of the substrate and a high internal reflection, from the side of the stack, low, which gives a brilliance and a brilliance providing an aesthetic effect particularly striking while retaining low internal reflection, so no mirror, and a tint in reflection meet commercial criteria. There is also a thickness of the second dielectric coating being in the preferred range provides more easily this aesthetic effect, particularly with a first thin dielectric coating. Example 3 also shows that with a first thick dielectric coating, but retaining a high ratio between the two dielectric films, one can get this aesthetic effect with a blue hue particularly strong, as shown by the strong negative coordinate value color b *.

The mechanical and chemical resistance of the glazing according to the invention are characterized by the transition successfully tests defined in the standard EN1096- 2 for said coatings of class B. In addition, the glazing according to the invention also meet the requirements of testing following:

salt spray (NSS: Neu al Salt Spray) according to ISO 9227-2006, preferably for at least 10 days;

in the climate chamber according to standard EN1036-2008, preferably for at least 10 days; and the Cleveland test according to ISO 6270-1: 1998, preferably for at least 10 days;

the acid resistance test (SO 2) according to EN 1096-2.

At AWRT test {Automatic web rub test) described below: A piston covered with a cotton fabric is contacted with the layer to be evaluated and oscillates on its surface. The piston carries a weight so as to apply a force of 33N on a finger 17 mm in diameter. The abrasion of the cotton over the coated surface will damage (remove) the coating after a certain number of cycles. The test is used to define the boundary before the layer will not fade (partial layer removal) and that the claws do not appear in the layer. The test is performed for 10, 50, 100, 250, 500 and 1000 cycles, at various separate locations on the sample. The sample is observed under an artificial sky to determine whether discoloration or scratches can be seen on the sample. AWRT The result indicates the number of cycles non or very little degradation (not visible to the naked eye under a uniform artificial sky at 80 cm from the sample).

test DBT (Dry Brush test) according to ASTM D2486-00 (Test Method "A"), preferably for at least 1000 cycles

and before and after optional heat treatment.

Of course, the invention is not limited to the embodiments described above.

Claims

1. Transparent solar control glazing comprising, on at least one of the faces of a glass substrate a transparent multilayer stack comprising a solar absorbing layer of at least 3 nm and a geometrical thickness of the first and second dielectric coatings framing said layer absorbing solar radiation, characterized in that the light reflection of the glass substrate coated with the multilayer stack measured from the substrate side is at least 20% and is at least twice the light reflection of the coated glass substrate the multilayer stack measured from the side of the stack, and in that the dyed substrate side has a reflection value of the color coordinate a * of less than 2 and a value of the color coordinate b * of less than 5.
2. Glazing according to claim 1, characterized in that the light reflection of the glass substrate coated with the multilayer stack measured from the substrate side is at least 2.5 times, preferably at least 3 times, and preferably of at least 3.5 times higher than the light reflectance of the glass substrate coated with the multilayer stack measured from the side of the stack.
3. Glazing according to any one of claims 1 or 2, characterized in that the light reflection measured substrate side is higher by at least 14%, preferably at least 20% and preferably at least 25%, the measured light reflection side stacking.
4. Glazing according to one of the preceding claims, characterized in that the measured light reflection of the substrate side is at least 27%, preferably at least 30%, and preferably at least 35%.
5. Glazing according to one of the preceding claims, characterized in that the second dielectric coating, disposed beyond the solar absorbing layer relative to the substrate, has a virtual total thickness L of between 35 and 85 nm, preferably between 40 and 70 nm, and advantageously between 55 and 65 nm, L being defined as the sum of the geometrical thicknesses (physical) in nm of each of the dielectric material forming the dielectric coating multiplied by the refractive index n 550 nm of each of the materials decreased by the refractive index of the gas from the surrounding atmosphere, and in that the refractive index n means the coating is greater than 1.5.
6. Glazing according to Claim 5, characterized in that the virtual thickness L of the first dielectric film, disposed between the substrate and the solar radiation absorbing layer is at least one and a half times thicker or thinner than the thickness virtual the last dielectric coating of the multilayer stack.
7. Glazing according to Claim 6, characterized in that the virtual thickness L of the first dielectric film, disposed between the substrate and the solar radiation absorbing layer is at least one and a half times thinner, preferably twice, and preferably three times, thinner than the virtual thickness L of the last dielectric coating of the multilayer stack.
8. Glazing according to any one of the preceding claims, characterized in that the second coating of dielectric material disposed above the solar radiation absorbing layer comprises a material having a high refractive index, higher than 2, preferably greater than 2.1.
9. Glazing according to claim 8, characterized in that the second coating of dielectric material disposed above the solar radiation absorbing layer comprises a mixture of titanium oxide and zirconium oxide or niobium.
10. Glazing according to any one of the preceding claims, characterized in that the solar absorbing layer is formed of a material having an average extinction coefficient between 380 nm and 750 nm, greater than 1.2, and preferably greater than 1.4.
11. Glazing according to any one of the preceding claims, characterized in that the solar absorbing layer comprises an alloy based NiCr and W, an alloy based on Cr and Zr, based on an alloy of W and Zr or an alloy based on W and Ta.
12. Glazing according to any one of the preceding claims, characterized in that the solar absorbing layer has a geometrical thickness of between 3 and 40 nm, preferably between 5 and 25 nm.
13. Glazing according to claim 12, characterized in that the solar absorbing layer has a geometrical thickness between 10 and 25 nm, and preferably between 12 and 22 nm.
14. Glazing according to any one of the preceding claims, characterized in that the two dielectric films sandwiching the solar absorbing layer is based on silicon nitride or aluminum nitride.
15. Glazing according to any one of the preceding claims, wherein the colorimetric change transmission, ΔΕ is less than 8, preferably less than 5, more preferably is less than 3, when said glass is subjected to a temperature of at least 630 ° C and up to 670 ° C for 7 minutes.
16. Glazing according to any preceding claim including color variation in reflection side face of the substrate, AE * rg is less than 8, preferably less than 5, more preferably is less than 3, when said glass is subjected to a temperature of at least 630 ° C and at most 670 ° C for 7 minutes.
17. Use of a solar control glazing according to any one of the preceding claims as glazed element for a motor vehicle, such as building glazing element or glazed element of a household appliance such as a cooking oven door.
PCT/EP2014/063634 2013-06-27 2014-06-27 Solar protection glazing WO2014207171A1 (en)

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EP14733191.2A EP3013763A1 (en) 2013-06-27 2014-06-27 Solar protection glazing
US14/901,193 US9944553B2 (en) 2013-06-27 2014-06-27 Solar protection glazing
CN201480036012.8A CN105339321A (en) 2013-06-27 2014-06-27 Solar protection glazing
EA201591946A EA031932B1 (en) 2013-06-27 2014-06-27 Solar protection glazing element
BR112015032242A BR112015032242A2 (en) 2013-06-27 2014-06-27 anti-solar glass
MX2015017428A MX2015017428A (en) 2013-06-27 2014-06-27 Solar protection glazing.
AU2014301013A AU2014301013B2 (en) 2013-06-27 2014-06-27 Solar protection glazing
JP2016522522A JP6367935B2 (en) 2013-06-27 2014-06-27 Solar protection glazing
SG11201509888XA SG11201509888XA (en) 2013-06-27 2014-06-27 Solar protection glazing
PH12015502830A PH12015502830A1 (en) 2013-06-27 2015-12-18 Solar protection glazing

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